EP1789485B1 - Fire-retarding sheet material having a metallic effect - Google Patents

Fire-retarding sheet material having a metallic effect Download PDF

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Publication number
EP1789485B1
EP1789485B1 EP05750672A EP05750672A EP1789485B1 EP 1789485 B1 EP1789485 B1 EP 1789485B1 EP 05750672 A EP05750672 A EP 05750672A EP 05750672 A EP05750672 A EP 05750672A EP 1789485 B1 EP1789485 B1 EP 1789485B1
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EP
European Patent Office
Prior art keywords
flame
pigment
iriodin
retardant
ppsu
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Not-in-force
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EP05750672A
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German (de)
French (fr)
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EP1789485A1 (en
Inventor
Detlef Bumann
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Roehm GmbH Darmstadt
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Evonik Roehm GmbH
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Priority to PL05750672T priority Critical patent/PL1789485T3/en
Publication of EP1789485A1 publication Critical patent/EP1789485A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/06—Polysulfones; Polyethersulfones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2481/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2481/06—Polysulfones; Polyethersulfones

Definitions

  • the invention relates to plastic moldings having a metallic surface and find their use in the interior of aircraft.
  • Plastic moldings for the interior of aircraft are known and marketed under the name europlex ® F and europlex ® PPSU by Röhm GmbH & Co. KG in the trade.
  • Europlex ® F are matte dyed, impact-resistant, flame-retardant polycarbonate (PC) grades
  • Europlex ® PPSU are also muted-colored, impact-resistant, polyphenylsulphone (PPSU) compliant with the OSU 65/65 test (Heat Release test according to FAR 25.853).
  • PC complies with FAR 25.853 (a) (1) (i), (a) (1) (ii), smoke density and toxicity requirements, PPSU also complies with FAR 25.853 (c).
  • the panels are supplied in thicknesses of 0.8 mm - 8.0 mm, the maximum width is 1,400 mm.
  • Seat panels, trays, door and door frame covers and lamp housings are manufactured from the panels.
  • the objects are achieved by a flame-retardant plastics molding based on transparent, flame-retardant PC and PPSU molding compositions with metallic-looking surface, a pigment Iriodin ® plus possibly influencing coloring colorants are used as the pigment.
  • Suitable plastics for the plastic molding are, in addition to transparent flame-retardant polycarbonate (PC), also polysulfones (PSU), polyphenylsulphone (PPSU) and polyethersulfones (PES) (manufacturer: Bayer AG, BASF, Solvay).
  • PC transparent flame-retardant polycarbonate
  • PSU polysulfones
  • PPSU polyphenylsulphone
  • PES polyethersulfones
  • the pigments Iriodin ® are brought by Merck KGaA in the trade.
  • the incorporation of the Iriodin ® pigments takes place for example in the form of a masterbatch from the corresponding plastic and the pigment Iriodin ®.
  • the masterbatch consists of 2 - 50 wt .-% Iriodin ® pigment, the rest is plastic granules.
  • the customary auxiliaries or coloring colorants can be added.
  • the extrusion of the composition according to the invention into plates is carried out on a conventional extruder.
  • the melt temperature is in the case of PPSU about 350 ° - 380 ° C, the temperature of the calender about 180 ° C, in the case of polycarbonate, the melt temperature is about 270 - 280 ° C and the calender approx 120 ° C.
  • the plastic molding can be further formed by conventional methods such as thermoforming or thermoforming.
  • Iriodin ® pigment color By varying the concentration of Iriodin ® pigment color and the metals gold, silver, or copper Altsilber can be represented.
  • Example 4 In the same mixture as in Example 1, a commercially available metal cut powder (metallic pigment) was incorporated and extruded into sheets of 1.5 mm thickness in Example 4 instead of Iriodin ®.
  • Example 4 The same mixture, also metal pigment, as in Example 4 was extruded into 1.5 mm thick plates.
  • HR limit HRR limit example sample (KW min / m 2 ) (KW / m 2 ) Requirements are: 1 1 17.21 52.22 Fulfills 2 22.63 48.04 3 4.66 34.27 2 1 16,80 37.48 Fulfills 2 10,95 22.64 3 33,60 41.08 3 1 - 5.92 50.03 Fulfills 2 - 0.45 58.59 3 - 3,30 56.94 Vergl.bsp. 4 1 144.68 157.73 Not fulfilled 2 125.28 137.70 3 144.15 162.67 Vergl.bsp. 5 1 158.63 154.31 Not fulfilled 2 173.26 179.95 3 123.61 131.62

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

Flame-retardant plastics mouldings composed of polyphenyl sulphones (PPSUs) or of polycarbonates (PCs) are coloured with Iridoin® pigments in such a way as to have a metallic effect. The effect is resistant to the usual stresses present in an aircraft cabin and complies with the respective fire-protection requirements.

Description

Gebiet der ErfindungField of the invention

Die Erfindung betrifft Kunststoffformkörper, die eine Metallicoberfläche aufweisen und ihre Verwendung beim Innenausbau von Luftfahrzeugen finden.The invention relates to plastic moldings having a metallic surface and find their use in the interior of aircraft.

Stand der TechnikState of the art

Kunststoffformkörper für den Innenausbau von Luftfahrzeugen sind bekannt und werden unter dem Namen Europlex® F und Europlex® PPSU von der Röhm GmbH & Co. KG in den Handel gebracht.Plastic moldings for the interior of aircraft are known and marketed under the name europlex ® F and europlex ® PPSU by Röhm GmbH & Co. KG in the trade.

Bei Europlex® F handelt es sich um gedeckt eingefärbte schlagzähe, flammgeschützte Polycarbonat (PC)-Typen, bei Europlex® PPSU handelt es sich ebenfalls um gedeckt eingefärbte schlagzähe, flammgeschützte Polyphenylsulphone (PPSU), die den OSU 65/65-Test erfüllen (Heat Release-Test gemäß FAR 25.853). PC erfüllt die FAR 25.853 (a) (1) (i), (a) (1) (ii) sowie die Anforderungen hinsichtlich Rauchdichte und Toxizität, PPSU erfüllt zusätzlich die FAR 25.853 (c).Europlex ® F are matte dyed, impact-resistant, flame-retardant polycarbonate (PC) grades, Europlex ® PPSU are also muted-colored, impact-resistant, polyphenylsulphone (PPSU) compliant with the OSU 65/65 test (Heat Release test according to FAR 25.853). PC complies with FAR 25.853 (a) (1) (i), (a) (1) (ii), smoke density and toxicity requirements, PPSU also complies with FAR 25.853 (c).

Die Tafeln werden in Dicken von 0,8 mm - 8,0 mm geliefert, die Breite beträgt maximal 1.400 mm. Aus den Tafeln werden u. a. Sitzverkleidungen, Tabletts, Tür- und Türrahmenabdeckungen und Lampengehäuse gefertigt.The panels are supplied in thicknesses of 0.8 mm - 8.0 mm, the maximum width is 1,400 mm. Seat panels, trays, door and door frame covers and lamp housings are manufactured from the panels.

Aufgabetask

Bisher waren Metallic-Lackierungen üblich, um die gedeckten, auf nicht transparenten Formmassen basierenden Kunststoffformkörper aus Europlex® F oder Europlex® PPSU mit Metallic-Dekor zu versehen. Lackierungen haben aber den Nachteil, nicht allzu kratz- und stoßfest zu sein, so dass die lackierten Gegenstände im Alltagsbetrieb der Flugzeugkabine schnell unansehnlich werden.So far, metallic coatings were customary to provide the covered, based on non-transparent molding compositions plastic moldings of Europlex ® F or Europlex ® PPSU with metallic decor. Paint finishes, however, have the disadvantage of not being too scratch- and impact-resistant, so that the painted objects quickly become unsightly in everyday operation of the aircraft cabin.

Die Verwendung von herkömmlichen Metallpigmenten in gedeckten oder opaken Basisformmassen erzielt naturgemäß nicht den Effekt einer Lackierung. Darüber hinaus verschlechtern herkömmliche Metallic-Pigmente auf der Basis von feingemahlenen Metallteilchen aufgrund ihrer Dochtwirkung das Brandverhalten der damit ausgerüsteten Kunststoffformkörper.The use of conventional metal pigments in opaque or opaque base molding materials naturally does not achieve the effect of a coating. In addition, conventional metallic pigments based on finely ground metal particles deteriorate the fire behavior of the plastic moldings equipped therewith due to their wicking action.

Aufgabetask

Es bestand daher die Aufgabe, eine Formmasse mit z. B. typischem Metallic-Effekt für Kunststoffformkörper zu entwickeln, die die Brandeigenschaften der Kunststoffformkörper nicht so verschlechtert, dass diese Kunststoffformkörper nicht im Flugzeugausbau eingesetzt werden können. Darüber hinaus sollte die Metallic-OberFläche robust gegen die üblichen Beanspruchungen in einer Flugzeugkabine sein. Der Farbeindruck der Metallic-Oberfläche sollte z. B. den Tönen RAL 9006/9007 entsprechen. Die verwendeten Pigmente sollten bei der Verarbeitungstemperatur von PPSU (ca. 350° C - 380° C Schneckentemperatur bei der Extrusion) stabil sein.It was therefore the task of a molding compound with z. B. typical metallic effect for plastic moldings that does not deteriorate the fire properties of the plastic moldings so that these plastic moldings can not be used in aircraft development. In addition, the metallic surface should be robust against the usual stresses in an aircraft cabin. The color impression of the metallic surface should z. B. correspond to the tones RAL 9006/9007. The pigments used should be stable at the processing temperature of PPSU (about 350 ° C - 380 ° C screw extrusion temperature).

Mit gedeckt eingefärbten Basismaterialien (oder opak) wird keine hinreichende Metallic-Wirkung erzielt (Effekt wird abgedeckt). Auf Basis transparenter BasisFormmassen ist die Ausgangssituation besser, jedoch existiert das Problem der Beeinflussung des Brandverhaltens auch hier.Covered colored base materials (or opaque) do not produce a sufficient metallic effect (effect is covered). Based on transparent base molding compounds the initial situation is better, but the problem of influencing the fire behavior also exists here.

Lösungsolution

Die Aufgaben werden durch einen flammgeschützten Kunststoffformkörper basierend auf transparenten, flammgeschützten PC und PPSU-Formmassen mit metallisch wirkender Oberfläche gelöst, wobei als Pigment ein Iriodin®-Pigment plus ggf. farbtonbeeinflussende Farbmittel verwendet werden.The objects are achieved by a flame-retardant plastics molding based on transparent, flame-retardant PC and PPSU molding compositions with metallic-looking surface, a pigment Iriodin ® plus possibly influencing coloring colorants are used as the pigment.

Ausführung der ErfindungEmbodiment of the invention

Als Kunststoffe für den Kunststoffformkörper kommen neben transparentem flammgeschützten Polycarbonat (PC) auch Polysulfone (PSU), Polyphenylsulphone (PPSU) und Polyethersulfone (PES) in Betracht (Hersteller: Bayer AG, BASF, Solvay).Suitable plastics for the plastic molding are, in addition to transparent flame-retardant polycarbonate (PC), also polysulfones (PSU), polyphenylsulphone (PPSU) and polyethersulfones (PES) (manufacturer: Bayer AG, BASF, Solvay).

Die Pigmente Iriodin® werden von der Merck KGaA in den Handel gebracht.The pigments Iriodin ® are brought by Merck KGaA in the trade.

Die Einarbeitung der Iriodin®-Pigmente erfolgt beispielsweise in Form eines Masterbatches aus dem entsprechenden Kunststoff und dem Iriodin®-Pigment. Der Masterbatch besteht aus 2 - 50 Gew.-% Iriodin®-Pigment, der Rest ist Kunststoffgranulat. Gegebenenfalls können noch die üblichen Hilfsstoffe oder farbgebende Farbmittel zugefügt werden.The incorporation of the Iriodin ® pigments takes place for example in the form of a masterbatch from the corresponding plastic and the pigment Iriodin ®. The masterbatch consists of 2 - 50 wt .-% Iriodin ® pigment, the rest is plastic granules. Optionally, the customary auxiliaries or coloring colorants can be added.

Zur Extrusion des Kunststoffformkörpers wird soviel Masterbatch zur Kunststoffformmasse hinzugegeben, dass die Menge an Iriodin®-Pigment der in der Rezeptur vorgegebenen Menge entspricht.For the extrusion of the plastic molded body as much masterbatch is added to the plastics molding composition, that the amount of pigment Iriodin ® in the formulation of the predetermined quantity.

Die Extrusion der erfindungsgemäßen Zusammensetzung zu Platten erfolgt auf einem üblichen Extruder.
Die Schmelzetemperatur beträgt im Fall von PPSU ca. 350° - 380° C, die Temperatur des Glättwerks ca. 180° C, im Falle von Polycarbonat beträgt die Schmelzetemperatur ca. 270 - 280° C und die des Glättwerks ca. 120° C.The extrusion of the composition according to the invention into plates is carried out on a conventional extruder.
The melt temperature is in the case of PPSU about 350 ° - 380 ° C, the temperature of the calender about 180 ° C, in the case of polycarbonate, the melt temperature is about 270 - 280 ° C and the calender approx 120 ° C.

Der Kunststoffformkörper kann durch übliche Verfahren wie Tiefziehen oder Thermoformen weiter umgeformt werden.The plastic molding can be further formed by conventional methods such as thermoforming or thermoforming.

Durch Variation der Konzentration von Iriodin®-Pigment und Farbe können die Metalle Gold, Silber, Altsilber oder Kupfer dargestellt werden.By varying the concentration of Iriodin ® pigment color and the metals gold, silver, or copper Altsilber can be represented.

Beispiele:Examples: Beispiel 1example 1 Zusammensetzungcomposition

PPSU-Formmasse, transparentPPSU molding compound, transparent 98,799 %98.799% (Europlex PPSU 99470)(Europlex PPSU 99470) Iriodin 123 hellglanzsatinIriodin 123 bright luster satin 1 %1 % Colortek OT-0005-BONColortek OT-0005-BON 0,2 %0.2% Printex® 60 (Degussa)Printex ® 60 (Degussa) 0,001 %0.001%

Aus der Mischung wurden 1,5 mm dicke Platten extrudiert.From the mixture, 1.5 mm thick sheets were extruded.

Beispiel 2Example 2

Aus der gleichen Mischung wie in Beispiel 1 wurden 1 mm dicke Platten extrudiert.From the same mixture as in Example 1, 1 mm thick sheets were extruded.

Beispiel 3Example 3

Aus der gleichen Mischung wie im Beispiel 1 wurden 2,0 mm dicke Platten extrudiert.From the same mixture as in Example 1, 2.0 mm thick sheets were extruded.

Vergleichsbeispiel 4Comparative Example 4 Zusammensetzungcomposition

PPSU-Formmasse, transparentPPSU molding compound, transparent 99,00 %99.00% (Europlex PPSU 99470)(Europlex PPSU 99470) Metallpigmentmetallic pigment 1,0 %1.0%

In die gleiche Mischung wie in Beispiel 1 wurde in Beispiel 4 anstelle von Iriodin® ein kommerziell erhältliches Metallschliffpulver (Metallpigment) eingearbeitet und zu Platten von 1,5 mm Dicke extrudiert.In the same mixture as in Example 1, a commercially available metal cut powder (metallic pigment) was incorporated and extruded into sheets of 1.5 mm thickness in Example 4 instead of Iriodin ®.

Vergleichsbeispiel 5Comparative Example 5

Die gleiche Mischung, auch Metallpigment, wie in Beispiel 4 wurde zu 1,5 mm dicken Platten extrudiert.The same mixture, also metal pigment, as in Example 4 was extruded into 1.5 mm thick plates.

Ergebnisse des Wärmeentwicklungstests nach FAR 25.853Results of the heat development test according to FAR 25.853

HR-GrenzwertHR limit HRR-GrenzwertHRR limit Beispielexample Probesample (KW min/m2)(KW min / m 2 ) (KW/m2)(KW / m 2 ) Anforderungen sind:Requirements are: 11 11 17,2117.21 52,2252.22 ErfülltFulfills 22 22,6322.63 48,0448.04 33 4,664.66 34,2734.27 22 11 16,8016,80 37,4837.48 ErfülltFulfills 22 10,9510,95 22,6422.64 33 33,6033,60 41,0841.08 33 11 - 5,92- 5.92 50,0350.03 ErfülltFulfills 22 - 0,45- 0.45 58,5958.59 33 - 3,30- 3,30 56,9456.94 Vergl.bsp. 4Vergl.bsp. 4 11 144,68144.68 157,73157.73 Nicht erfülltNot fulfilled 22 125,28125.28 137,70137.70 33 144,15144.15 162,67162.67 Vergl.bsp. 5Vergl.bsp. 5 11 158,63158.63 154,31154.31 Nicht erfülltNot fulfilled 22 173,26173.26 179,95179.95 33 123,61123.61 131,62131.62

Die Wärmeentwicklung der Proben (gemessen in KW min/m2 / KW/m2) bleibt bei Verwendung der erfindungsgemäßen Zusammensetzung deutlich unter den vorgeschriebenen Grenzwerten von 65/65 KW min/m2 / KW/m2 (HR/HRR).The heat development of the samples (measured in KW min / m 2 / KW / m 2 ) remains when using the composition of the invention significantly below the prescribed limits of 65/65 KW min / m 2 / KW / m 2 (HR / HRR).

Claims (6)

  1. Flame-retardant plastics moulding composed of transparent, flame-retardant polycarbonate (PC) or polyphenyl sulphone (PPSU) with metallic-effect surface,
    characterized in that
    the pigment used comprises an Iriodin® pigment.
  2. Flame-retardant plastics moulding according to Claim 1,
    characterized in that
    the amounts of Iriodin® pigment, based on the moulding composition from which the plastics moulding is produced, are from 0.1 to 10% by weight.
  3. Process for production of a flame-retardant plastics moulding according to Claim 1,
    characterized in that
    the required amount of Iriodin® pigment in a masterbatch is added to the moulding composition and is extruded in a manner known per se to give plastics mouldings.
  4. Process according to Claim 3,
    characterized in that
    the thickness of the plastics moulding is from 1.0 to 12 mm.
  5. Flame-retardant plastics moulding according to Claim 1,
    characterized in that
    its perceived colour is in accordance with RAL 9007 HR.
  6. Flame-retardant plastics moulding according to Claim 1,
    characterized in that
    its perceived colour is in accordance with RAL 9006 HR.
EP05750672A 2004-08-30 2005-06-16 Fire-retarding sheet material having a metallic effect Not-in-force EP1789485B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL05750672T PL1789485T3 (en) 2004-08-30 2005-06-16 Fire-retarding sheet material having a metallic effect

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004042095A DE102004042095A1 (en) 2004-08-30 2004-08-30 Flame retardant plate materials with metallic effect
PCT/EP2005/006452 WO2006024331A1 (en) 2004-08-30 2005-06-16 Fire-retarding sheet material having a metallic effect

Publications (2)

Publication Number Publication Date
EP1789485A1 EP1789485A1 (en) 2007-05-30
EP1789485B1 true EP1789485B1 (en) 2008-11-05

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US (1) US8303864B2 (en)
EP (1) EP1789485B1 (en)
JP (1) JP4838801B2 (en)
KR (2) KR100914804B1 (en)
CN (1) CN1957028B (en)
AT (1) ATE413429T1 (en)
AU (1) AU2005279502A1 (en)
BR (1) BRPI0514754A (en)
CA (1) CA2570290C (en)
DE (2) DE102004042095A1 (en)
DK (1) DK1789485T3 (en)
ES (1) ES2317248T3 (en)
HK (1) HK1104311A1 (en)
PL (1) PL1789485T3 (en)
RU (1) RU2382797C2 (en)
TW (1) TWI298727B (en)
WO (1) WO2006024331A1 (en)
ZA (1) ZA200701734B (en)

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JP4838801B2 (en) 2011-12-14
KR100914804B1 (en) 2009-09-02
CA2570290C (en) 2011-08-23
JP2008511696A (en) 2008-04-17
AU2005279502A1 (en) 2006-03-09
RU2007111554A (en) 2008-10-10
KR20070051870A (en) 2007-05-18
US20070228342A1 (en) 2007-10-04
BRPI0514754A (en) 2008-06-24
PL1789485T3 (en) 2009-04-30
ZA200701734B (en) 2008-08-27
DE502005005907D1 (en) 2008-12-18
WO2006024331A1 (en) 2006-03-09
ES2317248T3 (en) 2009-04-16
KR20080108355A (en) 2008-12-12
CN1957028B (en) 2012-02-22
TWI298727B (en) 2008-07-11
EP1789485A1 (en) 2007-05-30
US8303864B2 (en) 2012-11-06
CN1957028A (en) 2007-05-02
RU2382797C2 (en) 2010-02-27
ATE413429T1 (en) 2008-11-15
HK1104311A1 (en) 2008-01-11

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